Process for breaking petroleum emulsions



Patented May 25, 1954 UNITED STATES PATENT OFFICE PROCESS FOR BREAKINGPETROLEUM EMULSIONS corporation of Delaware No Drawing. Application June27, 1952 Serial No. 296,083

14 Claims.

This invention relates to processes or procedures particularly adaptedfor preventing, breaking or resolving emulsions of the waterin-oil type,and particularly petroleum emulsions.

The present invention is a continuation-inpart of my co-pendingapplication, Serial No. 288,742, filed May 19, 1952.

My invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type, that are commonly referredto as cut oil, roily oil, emulsified oil, etc., and which comprises finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

The demulsifying agents employed in the present demulsifying process arethe products obtained by the process of condensing (a) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, lowstage phenol-aldehyde resin of thetype described hereinafter as component (a) in Part 1; (b) a basicnonhydroxylated secondary monoamine having not more than 32 carbon atomsin any group attached to the amino nitrogen atom, and formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the water-in-oil type, Iparticularly prefer to use those which as such or in the form of thefree base or hydrate, i. e., combination with water or particularly inthe form of a low molal organic acid such as the acetate or hydroxyacetate, have sufiiciently hydrophile character to at least meet thetest set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to DeGroote et al. In said patent such test for emulsification using awater-insoluble solvent, generally xylene, is described as an index ofsurface activity.

In the present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in 5 many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

Reference is again made to U. S. Patent No.

2,499,368 dated March 7, 1950, to De Groote and Keiser. In saidimmediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylenewater emulsion. A suitable procedureis as fol- 0 lows: The oxyalkylated resin is dissolved in an equalWeight of xylene. Such 50-50 solution is then mixed with 1-3 volumes ofwater and shaken e to produce an emulsion. The amount of xylene isinvariably sufficient to reduce even a tacky resinous product to asolution which is readily dispersible. The emulsions so produced areusually xylene-in-water emulsions (oil-in-water type) particularly whenthe amount of distilled water used is at least slightly in excess of thevolume of xylenesolution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awater-inxylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and further dilution with water.

"If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 units per resin molecule. Such resin, when diluted with anincipient self-emulsification -or water even in .presence of testsemploy a xylene solution-produces a sol=or'whether it-merely-proequalweight of xylene, will serve to illustrate the above emulsificationtest.

In a few instances, the resin may not be sufficiently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposeof this test.

In many cases, there isrno rdoubt-ias toT'the presence or absence ofhydrophile or surfaceactive characteristics in theproductsused-inaccordance with this invention. Theyidissolve or disperse inwater; and such dispersions foam readily. With borderline cases, i. e.,those which show only incipient hydrophile or surface active property(sub-surface-activity) tests 'for emulsifying properties orse1f-dispersibility =;are useful. The fact that a reagent is capable ofproducing a dispersion is'distinctly hydrophile. Indoubtful cases,comparison can be made withthe butylphenol-formaldehyderesin analogwherein 2.moles.of ethylene oxide have been introduced for each phenolicnucleus.

Thepresence otxyleneor an equivalent waterinsoluble solvent may mask thepoint .at which a solvent-free product onniere dilution. in a testtubeexhibits self-emulsification. For this .reason, if .it is desirableto. determine the. approximate, point .where self-.emulsificationbegins, then .it is better to eliminate the xylene or equivalentfromasmall portion of thereaction mixture and (test .such.;portion. ..Insomecases, such xylenefreeresultant .mayshow initial or incipient hyv,drophileproperties, whereas in presence of xylene such properties wouldnot vbe noted. In other cases,.the. first objective indication ofhydrophile properties maybe the capacity-of the material to emulsify, aninsoluble solventsuchras xylene. It is .to. ,be emphasized that,hydrophile properties herein referred to. areisuchsas thosezexhibitedby the presence of emulsifying properties ,and gothrough .the range ,of.homogeneous .dispersibility or admixture with added. .water-rinsolublesolvent and minor proportions of common electrolytes as occur in oilfield brines.

Elsewhere, it is pointed outthatuan emulsi fication test may .be..usedto determine ranges of 'surface activity and that :such. em'ulsiflcation"solution. Stated. another it is* 'really "-immaterial whether" a xylene-,duces an emulsion.

For convenience, what is said hereinafter will he divided into "fiveparts:

: :Part lwis'the introductory part as far asithe ddemulsifying .agentsthemselves are concerned,

i. 8., lthe,,.amineemodified resins;

; Part 2.is ooncerned with the :general structure...of.lthe-:amine-modified resin and aalsoithecresin ,itself,.-which;isused-as a raw-material;

.. Part 3,-is concerned with appropriate basicisec-i ondary amines freefrom a hydroxylradical which ,maybe employedin thepreparationof theherein described amine-modified resins;

Part 4. is concerned with the .reactionsinvolving .thev resin, theamine,and iormaldehyde -,to .produce the specific products or compounds; .and

Part 5 iscOncerned withtheauseof-the aminemodified resins obtained asadescribed in Part 4 .for the resolutionofemulsions of the .watereineoil,type.

70 carbon atoms, and-en generally :is a

4 PART 1 As previously stated, this invention is concerned with the useas demulsifiers for resolution q or breaking of petroleum emulsions ofthe water- L .qin-loil-e type 's'ofscertain amineemodifi'ed resins.

Such "aminem'odified resins have'lbeen' described in the aforementionedcopending application, *Serial No. 288,742, filed May 19, 1952.

The zdemulsifying agents are heat-stable oxyalkylation susceptibleresinous condensation products of (a) a defined phenol-aldehyde resin,

"(by a--basio -ndnhydroxylated secondary monoamine having notmore than32 carbon atoms in to the amino nitrogen atom, ;-=.and--(c)',-formaldehyde. The condensation reac- ;tion:iis conducted at atemperature sufficiently highcto eliminate water and below the pyrolyticpoint of the reactantsrand the resultants of rein water is proofythat it99 action. Another aspect of the invention, of

course, is the procdure-employed -for "making such-condensationproducts.

The phenol-aldehyde resin designated as com- -ponent "(00) "is 'anoxyalkylationsusceptible, fusible, nonoxygenated-organicsolvent-soluble,

" water-insoluble, low-stagephenol-aldehyde resin having "an average:molecular weight corresponding to at least 3 and-not'over- 6 phenolicnuclei per resinmolecule. The phenol-aldehyde-resin m isdifuncti'onal'only in regard to methylol-forming reactivity;andthe--resin--is"derived-'by reac- -tion between a difunctionalmonohydric phenol and an'aldehyde having not over 8 carbon atoms andreactive toward thepheno l. -Also; the resin is 95 formed inthesubstantial absence of-triiunctional phenols. ThephenolconStituent-oftheresin'is of the formula:

having at .least 4 carbon atoms'andnotmore than "*24'carbon atoms;*andsubstitutectin' the 2,4,6 po- 'sition.

This invention in; a "more, limited aspect 'relates to :the use asdemulsifiers of certain :ar'nine-m'odif'fied thermoplasticphenol-aldehyde resins. For purpose of simplicity the invention, asfaras demulsifrcation is concerned;.may be typified'by ref erence-to, theresinous "materials themselves. These resins maybe exemplified by anidealized *formula which "may,'in part, be an sever-simplification in'aneffortto'present certain resin struc- "ture. .Such formula :Would be.the following:

L; an

gob

in which ;R :representsan: aliphatic hydrocarbon substituent generally=havingrfour and'not over1l8 carbon-atoms-but amost preferably: notover.- :14 small whole number varying from 1-to.4. .-.-In the resinstrucsturerit is-shownas being derived iirom formaldehydetrzalthoughobviously aother: aldehydes are .equallmsatisfactory. r l haaami-ne.residue in :the

abovestructureds,derivedfrom atbasic amine," and usually a stronglybasic amine, and may be indicated thus:

in which R represents any appropriate hydrocarbon radical, such as analkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals.The only limitation is that the radical should not be a negativeradical, which considerably reduces the basicity of the amine, such asan aryl radical or an acyl radical. Needless to say, the two 00-currences of R may jointly represent a single divalent radical insteadof two monovalent radicals. This is illustrated by morpholine andpiperidine. The introduction of two such amino radicals into acomparatively small resin molecule, for instance, one having 3 to 6phenolic nuclei as specified, alters the resultant product in a numberof ways. nitrogen atom, of course, adds a hydrophile effect; in thesecond place, depending on the size of the radical R, there may be acounterbalancing hydrophobe effect or one in which the hydrophobe effectmore than counterbalances the hydrophile effect of the nitrogen atom.Finally, in such cases where R contains one or more oxygen atoms,another effect is introduced, particularly another hydrophile efiect.

Combinations, resinous or otherwise, have been prepared from phenols,aldehydes, and reactive amines, particularly amines having secondaryamino groups. Generally speaking, such materials have fallen into threeclasses; the first represents non-resinous combinations derived fromphenols as such; the second class represents resins which are usuallyinsoluble and used for the purpose for which ordinary resins,particularly thermo-setting resins are adapted. The third classrepresents resins which are soluble as initially prepared but are notheat-stable, i. e., they are heat-convertible, which means they are notparticularly suited as raw materials for subsequent chemical reactionwhich requires temperatures above the boiling point of water orthereabouts.

The third class of material which of the three classes mentionedapproaches the closest to the herein-described derivatives or resinousamino derivatives is described in U. S. Patent No. 2,031,557, datedFebruary 18, 1936, to Bruson. The procedure described in said Brusonpatent apparently is concerned with the use of monoamines only.

The resins employed as raw materials in the instant procedure arecharacterized by the presence of an aliphatic radical in the ortho orpara position, i. e., the phenols themselve are difunctional phenols.This is a diiferentiation from the resins described in theaforementioned Bruson patent, No. 2,031,557, insofar that said patentdiscloses suitable resins obtained from meta-substituted phenols,hydroxybenzene, resorcinol, p,p' (dihydroxydiphenyl) -dimethylmethane,and the like, all of which have at least three points of reaction perphenolic nuclei and as a result can yield resins which may be at leastincipiently cross-linked even though they are apparently still solublein oxygenated organic solvents or else are heat-reactive insofar thatthey may approach insolubility or become insoluble due to the efiect ofheat, or added formaldehyde, or both.

The resins herein employed contain only two terminal groups which arereactive to formaldehyde, i. e., they are difunctional from the stand-In the first place, a basic point of methylol-forming reactions. As iswell known, although phenols, and depending on the procedure employed,one may obtain cross-linking which indicates that one or more of thephenolic nuclei have been converted from a difunctional redical to atrifunctional radical, or in terms of the resin, the molecule as a wholehas a methylol-forming reactivity greater than 2. Such shift can takeplace after the resin has been formed or during resin formation.Briefly, an example is simply where an alkyl radical, such as methyl,ethyl, propyl, butyl, or the like, shifts from an ortho position to ameta position, or from a para position to 2, meta position. Forinstance, in the case of phenol-aldehyde varnish resins, one can preparat least some in which the resins, instead of havin only two points ofreaction can havev three, and possibly more points of reaction, withformaldehyde, or any other reactant which tends to form a methylol orsubstituted methylol group.

Apparently there is no similar limitation in regard to the resinsemployed in the aforementioned Bruson Patent 2,031,557, for the reasonthat one may prepare suitable resins from phenols of the kind alreadyspecified which invariably and inevitably would yield a resin having afunctionality greater than two in the ultimate resin molecule.

The resins herein employed are soluble in a non-oxygenated hydrocarbonsolvent, such as benzene or Xylene. As pointed out in the aforementionedBruson Patent 2,031,557, one of the objectives is to convert thephenol-aldehyde resins employed as raw materials in such a way as torender them hydrocarbon soluble, i. e., soluble in benzene. The originalresins of U. S. Patent 2,031,557, are selected on the basis ofsolubility in an oxygenated inert organic solvent, such as alcohol ordioxane. It is immaterial whether the resins here employed are solublein dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as raw materials must be comparatively lowmolal products having on the average 3 to 6 nuclei per resin molecule.The resins employed in the aforementioned U. S. Patent No. 2,031,557,apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the freebase or the salt, do not go over to the insoluble stage on heating. Thisapparently is not true of the materials described in aforementionedBruson Patent 2,031,557 and apparently one of the objectives with whichthe invention is concerned, is to obtain a heat-convertible condensationproduct. The condensation product obtained according to the presentinvention is heat stable and, in fact, one of its outstanding qualitiesis that it can be subjected to oxyalkylation, particularly oxyethylationor oxypropylation, under conventional conditions, i. e., presence of analkaline catalyst, for example, but in any event at a temperature aboveC. without becoming an insoluble mass.

Although these condensation products have been prepared primarily withthe thought in mind that they are precursors for subsequent reaction,yet as such and without further reaction, they have definitely valuableproperties and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularlywhen employed as a reactant for preparation of derivatives, is stillimportant from the standpoint of manufacture of the condensationproducts themselves insofar one may start with difunctional th e*difrfmmoicu es "are simir 4 volved although, for theoretical reasons,"less likely. What is saidherein in this respect is simply by way of exilanation to avoid any limitation in regard to the appended claims.

PART 2 It is wellkn'own' that one can readily urchase on'the' open"maflet',' onpr'epa'r'e, fusible, organic solvnflsoluhle; water-"insolubleresi'ri" polymers e; between' 20 C.andl00 C.,and'm re s15 5-: I TF PVQ FWpmximafied' an idealized llyat a'temoerature of 80 to 90 Q. There formby the mu I is s ch lim ation in e ndens t nrrq-c. OH 011 eda ihernldescr p r sr sqnsiw i f e' Ho o snve o wharnasbeen'said prevlp s 15 1%5% Wha is l id above; deserves" he n ii plifii fg i'e thi point f r thereasdn t it m ShbItell' ;W1 lat lSSaiI subsequentlyin rega' to B R A.the; production of"thej herein described conden' In the above formulajnrepresents'a small] hole nfbr 'd S, 'pfi ntedfjo tjinfthTinstant numbera n f o 1 tqfil 7 or 8, 9 o e; 1?

invention the' nl el ct d sxt'lenei rihe z' o p o l 1 1 2 1, $z 1 l e 1h?- nhee s'l v ob e o n erat r ehovjethebbi u. or a mete ffec n t e ex ml de a a 5 que t employ m e atures; es Wi h t i1' Ofi1C. If one wereusin ir'e ns oflf helk e l kid i U sB 't N9 2. 31 355? itlappearsjdesirable and perhaps absolutely; "necessary that emp a ure .b l n ire y10min "1 e lifli tllwh h" f i tia t er sfrom ms e i s .subi 'c tog h aunder a. Yawn?! employed in the aforemehtioried BruSOh Pat n't as j describedgi the i fl ,A mite s'uhi o.1 7- Sinc fo a h e. n ra l .:i nus it -ins n e 10W mel a eieht emfiloyed econ omicallylih a nj aqueouf sjpha e oolyrrlersiwhere the total nutrliberof phenol 0,%"I %4. ti n iorie am le) it. n ie sf. 19 V rie it m t ,6,1,i. e., n r e 'l'flpml j sary" to have m am facturipg procedurejywhich liq lift represents'analiphatichhydrocarhonsub-E v vill' allow reactions'to takeplace' atthiil terfi Stifilnt; generally 911 alkyllradicalha h g' om face o f thetw odrnrpiseihle liquids, to j witg the' 4 to is carbon atoms su'ch asaj h 1, farr1yl, formaldehyde solution'andthe resin solutiq lw'on hexyl,'d 'ecyl or dode'cyl radical, Wh the dithe assumption that generallythe'ami'ne will d valerit bridge radical" is shown asjb g' de d some-inone phase or the other; Although r 7 from formaldehydeit mem course, beder ve'fc ll actions of the kind hereinjdescribed will' begmj from anyother reactive aldehyde having 8 carat least at comparativelyiowtemperatures;; for bonatomsor less.

doe's fiot go to completion except by the use of notimean it isnecessarily sblub N v the higher; temperatures. Ifhe use 'of higheifsolj 'ent This parti; larl f true whe temperatures means of course, thattheconden; resins are derived fligllflj trijlllljotionfal p sationproduct obtained at the end of the re-f previously noted, I-Io tyev 1veri' when I actionmust'not beheat-reactive. Q f coursei onej 40 frorhadi iunctional phenol, ior inslt'a ce" can a dg anoxygenated-solventsuchas alcohol, phenylphenoLjone"may' optaih aresi dioxane; ariousethers iofiglycols; or the like, not luhl'e'in a nonoXygenatedfsolierit;.

ij rddi sf mq' neo hase; vl t s13 9:. e le ter procedur'eis employed inpreparingthe'here' solvent suc h as a lowj mo a1 alcohol; dio

injd'ejscrihedcondensations it is purely'a matter 4:. or' diethylglj'col 'diethylethr. Sometimes am of'conifehiencq but Whether it is or not,u1tifture of the two solvents (oxygenated'tfima np mately thetemperature must f stilljpas's withihl oxygenated)"willlserveJ SeeEXarripl'eQd of U, S. the zone indicated elsewherej' i. e1;s ornewl rrePatent Np}2499365}dated'March' 7, 1950'; to

abot' ie the'boili ng point of ater unlesssome 015- De Groot elandKeis'er.

vious e uivalent procedure is used. I A 'rhe "resins hereinciafs ravyinateitl sl Any; reference, as in the hereto appended; must he soliible ina,nonoxygenated solvent, such claims,- to the procedure employed intheprocess as henzene or xylene. This presentslnoprohlem' employed inthe manufael ireof the condense-i insofar that all that is required isto m'akla tio'flprod'uct is not intended to limit the metl iodlsolubility test on commercially available resins'f or orderin which thereactants fare added, cor

mingled or reacted] The procedurahjasfhef referred to asacondensationproces or opvio s I addthe' amine, and theria d'the'formal dehydel ophenol-aldehyde resin s'of th type notedas admberiiene-soluhle'asdescribed aforem'e'ntiorid' U. S. Patent No, $439,365] or in U. 8.Patent:

caflbe add'din any' order. I am inclined'tolf If o e"" e1ted af s n; of,the. kindfjust'de f believe that in the presencep'f a basic catalystdscribed prevg asi and reacted apfir o'giinately one such as the amineemployed, that'the f ormalde mole of theresinwith magne soriormaldehirde; hydaproduces methylol groups" attachedfiotlie 5 andtwomoles ofa' basidiionhydroic'yl'ated "se phenolic nuclei which, in turn;react" with the on'd'ar'y amine assbecifie'd, follciiki rlg the sameamine; It would be immateria'L'of 'coi'irsej'if the idealized"over-simplificationpreviously referred formaldehyde reacted withithe'amine so as to i to, theresultant producfmight' beillustrated introducea methylol' group attached" to" nitrogen; thus 1 which, in turn, wouldreactwith ther'es'inmole-' I cule.; Also, it would be immaterialif"both"typ es R"\' H f OH 03 R" each" other with 'theevolutio'n of'a'mole of forr r'i aldehyde available for "further reaction. Fur -1thermor'e, "a reaction cou1d"take'placeir1 which '75" R 11 B The basichydroxylated amine may be designed thus:

OH OH OH OH OH OH H H H H c-- -oo o H O H O n H in R R R As has beenpointed out previously, as far as the resin unit goes one can use a moleof aldehyde other than formaldehyde, such as acetaldehyde,propionaldehyde or butyraldehyde. The resin unit may be exemplifiedthus:

in which R is the divalent radical obtained from the particular aldehydeemployed to form R n R the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms ofthe method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previousl mentioned U. S. Patent,499,368. Resins can be made using an acid catalyst or basic catalyst ora catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although I have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as at 200th of apercent and as much as a few l 0ths of a percent. Sometimes' moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; forinstance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay b such that it corresponds to a fractional value for n, as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

TABLE I Example Number Mo]. Wt of Resin Molecule Position R derived of Rf yl tertiary butyl. tertiary amyL nonyl tertiary buty tertiary amyL. nn

o yl tertiary butyl tertiary amyl do non para.- do

cmounoecmo mmwmwiom sgcgk cpipawsn do do AFT? As has been pointed outpreviously, the amine re n' e ey s a re t nt is 'L- i eco ary monoamine,and preferably a strongly basic secondary monoamine, free-from hydroxylgroups whose composition is indicated thus: T

in which R represents a monovalent alkyl, alicyclic arylalkyl radicaland "may be heterocyclic in -a --few-instances"as in the case of""piperidine and a secondary "amine derived from'furfurylaminebwmethylation or ethylation; or a similar ro edu e a v,-

-Another examp e of a heterocyclic amine is, of course;-morpholine:-' dThe secondary amines most readily available arey-of course; amines suchas'dimethylamine, methylethylamine,- diethylamine, dipropylamine,ethylpropylarnine, dibutylam-ine, 'diamylamine, dihexylamine,dioctylamine,- and dinonylarnine. other 'ami-nes 'iiiicludesgis-dim u ya1)- erase-"There arefof eeu'r ,evd ee amines which canbe'r'eatedwi'tfi' an 'al'k lati'rig agent such as dimethyl sulfate, diethylsulfate, an alkyl bromide, an ester of sulfonic acid, etc., to producesuitable amines within the herein specified limitations. methylatealpha-methylbenzylamine, or benzylamine itself, to produce a suitablereactant. Needless to say, one can use secondary amines, such asdicyclohexylamine, dibutylamine or amines containing one cyclohexylgroup andone elk yrgreds sweetener; upj'and the alkyl group, such asethycycloh yFami'rie, ethylben- 'zylami'rifetc.

snot-nee class of amines which are particula ly desirable for the "reson" thatitheylintroe 'wr r a s ther liege are fo la in which :n is asmall whole number having a value of 1 or more, and maybe" as much as 10or 12; n is an'integer'having a'value'of' '2 "to 4; inclusive; mrepresents the numeral 1 to 2; and 7h" represents a number to '1', withthe proviso that the sum of m plus ml equals 2; and R has its priorsignificance, particularly as a hydrocarbon radical. E The preparationof such amines has been described in the literature andparticularly-:injtwo United States patentsfto wit. U; .i' re.-2;32 ;r4;dated August 8, 1944, to Silence. The latter patent describes typicalhaloalkyl ethers such {as n v QHaOC2H4C1 e1 oii-omooaaqmmm or witha'primary amine such as methylamine, ethylamine, cyclohexylamine;-etc'.; to produce a secondary amine of the kind above described, inwhich on'eofthe groups attached to nitrogenis For example, one can 55 tosomewhat similar 79 examples. Such haloalkyl ethers can react withammonia,

7,} Patent NO. 2,499,363.

ifsedby 51m he palky ste r l e. c

be' -reacted with" ammonia to "give secondary amines as described in thefirst of the two patents mentioned immediately preceding. Compounds soobtained are exemplified by s ee q qamisfl (CtfirzbCtzIJlfiOCzfIsCzI-R)zNH (clrreoonecmono 0 (one) cnone nn "iiiio cnzoneocnzoneoornon 21in(oneocrizcnecnzcnecmcm) ZNH other "s'o vi f at sin ier seeeiidei 'i fnine e w Blis ?fdffthlso ipo i o as described in U. s. Patent No.2,375,659, dated be obtained by alkylation of fcyclohexylmethylamine orthe alkylation of similar :primary amines, or, for that matter, aminesof the kind described in U. S. Patent No, 2,482,55i6, dated September20, 1949, to Kaszuba, provided there isino negative group or halogenattachdito the ;phenolic fn' ucleus. :Examme's 'iriludeithdffollowing:beta-phenoxyethylarr 'ine, gra Y maphe- "nbxypropylamine, 'beta phnoxy-alpha;-methy lethylam'inej and beta-phenoxypropylamine.

- Other suitable amines are the kind described processes employed in'themanufacture of the condensation productrepresent cogeneric mix- 5 tureswhich are the re'sulto'f a condensation refinal product of the cogenericmixture except in terms of the process itself. Previous reference hasbeen made to the fact .that the procedure herein employed is compar-"able," in a general way, to that which corresponds derivatives madeeither from phenols as differentiated from a resin, or in themanufacture of a phenol-amine-aldehyde resinj" or else from aparticularly selected resin and an amine and formaldehyde in the manner6!) described in Eruson Patent No. 2,031,557 in ordered ury 27, 194.3;to Hester; and 2.35 5337;

{5 peratures up to C. or thereabouts may be employed, it is obvious thatthe procedure becomes comparatively simple. Indeed, perhaps nodescription is necessary over and above What has been said previously,in light of subsequent However, for purpose of clarity the followingdetails are included.

,A convenient piece of equipment for preparationdf these cogenericmixtures is a resin pot offithe kind described in aforementioned U. S.In most instances the resin 'be used or one can use a 13 selected is notapt to be a fusible liquid at the early or low temperature stage ofreaction if employed as subsequently described; in fact, usually it isapt to be a solid at distinctly higher temperatures, for instance,ordinary room temperature. Thus, I have found it convenient to use asolvent and particularly one which can be removed readily at acomparatively moderate temperature, for instance, at 150 C. A suitablesolvent is usually benzene, xylene, or a comparable petroleumhydrocarbon or a mixture of such or similar solvents. Indeed, resinswhich are not soluble except in oxygenated solvents or mixturescontaining such solvents are not here included as raw materials. Thereaction can be conducted in such a way that the initial reaction, andperhaps the bulk of the reaction, takes place in a polyphase system.However, if desirable, one can use an oxygenated solvent such as alow-boiling al-cohcl, including ethyl alcohol, methyl alcohol, etc.Higher alcohols can comparatively nonvolatile solvent such as dioxane orthe diethylether of ethyleneglycol. One can also use a mixture ofbenzene or xylene and such oxygenated solvents. Note that the use ofsuch oxygenated solvent is not required in the sense that it is notnecessary to use an initial resin which is soluble only in an oxygenatedsolvent as just noted, and it is not necessary to have a single phasesystem for reaction.

Actually, water is apt to be present as a solvent for the reason that inmost cases aqueous formaldehyde is employed, which may be the commercialproduct which is approximately 37%, or it may be diluted down to about30% formaldehyde. However, para-formaldehyde can be used but it is moredifficult perhaps to add a solid material instead of the liquid solutionand, everything else being equal, the latter is apt to be moreeconomical. In any event, water is present as water of reaction. If thesolvent is. completely removed at the end of the process, no problem isinvolved if the material is used for any subsequent reaction. However,if the reaction mass is going to be subjected to some further reactionwhere the solvent may be objectionable, as in the case of ethyl or hexylalcohol, and if there is to be subsequent oxyalkylation,

then, obviously, the alcohol should not be used or else it should beremoved. The fact that an oxygenated solvent need not be employed, ofcourse, is an advantage for reasons stated.

Another factor, as vent goes, is whether or not the cogeneric mixtureobtained at the end of the reaction is to be used as such or in the saltform. The cogeneric mixtures obtained are apt to be solids or thickviscous liquids in which there is some change from the initial resinitself, particularly if some of the initial solvent is apt toremainwithout complete removal. Even if one starts with a resin which isalmost water-white in color, the products obtained are almost invariablya dark red in color or at least a red-amber, or some color whichincludes both an amber component and a reddish component. By and large,the melting point is apt to be lower and the products may be more stickyand more tacky than the original resin itself. Depending on the resinselected and on the amine selected the condensation product or reactionmass on a solvent-free basis may be hard, resinous and comparable to theresin itself. The products obtained, depending on the reactantsselected, may be water-insoluble or far as the selection ofsolwater-dispersible, or water-soluble, or close to being water-soluble.Water solubility is enhanced, of course, by making a solution in theacidified vehicle such as a dilute solution, for instance, a 5% solutionof hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also mayconvert the finished product into salts by simply adding astoichiometric amount of any selected acid and removing any waterpresent by refluxing with benzene or the like. In fact, the selection ofthe solvent employed may depend in part whether or not the product atthe completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminate all solvent, using a temperature of not over C.and employing vacuum, if required. This applies, of course, only tothose circumstances where it is desirable or necessary to remove thesolvent. Petroleum solvenis, aromatic solvents, etc., can be used. Theselection of solvent, such as benzene, xylene, or the like, dependsprimarily on cost, i. e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned: (a) is the solvent to remain in the reaction mass with- (b)is the reaction massto be subjected to further reaction in which thesolvent, for instance, an alcohol, either low boiling or high boiling,might interfere as in the a water-wash to remove the water-solubleunreacted formaldehyde, if any, or a water-wash to remove any unreactedlow molal soluble amine, if employed and present after reaction? anopportunity to proceed as far as it some low temperature, for instance,30

fact, it may be anything from a few hours up to 24 hours. I have notfound any case where it was necessary or even desirable to hold the lowtemperature stage for more than 24 hours. In fact, I am not convincedthere is any advantage in holding it at this stage for more than 3 or 4.hours at the most. This, again, is a matter of convenience largely forone reason. In heating and stirring the reaction mass there is atendency for formaldehyde to be lost. Thus, if the reaction can beconducted at a lower temperature so as to use up part of theformaldehyde at such lower temperature, then the amount of unreactedformaldehyde is decreased subsequently and makes it easier to preventany loss. again, this lower temperature is not necessary by virtue ofheat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theexit 4 2 2 wa -M- e s. dis r buti tent that. I r

"f h mingiormald'ehyde. Thismutual soli l 15 lis e e is ryjaa rev eu ined butlmay, .be'. I convenient under certain circumstances; n theother-hand, if the products are n t tuajlly soluble, then agitaticnshould be Qyigorious for the reason that reaction probitfls not solublein the resin solution it may be so ble in the a ueous formaldehydesolution. If

sof'the'resin then will dissolve in the formaldehyde solution as added,and if not, it is even possible th 1; the initial reaction mass could bea ithree phase system instead of a two-phase system although this wouldbe extremely unusual. This solution, or mechanical mixture, if notcomplet'elyj 'soluble is cooled to at least the reaction temperature orsomewhat below, for example 35 C, or slightly lower, provided thisinitial .low temperature stageis'ernployed. The formaldehyde is thenadded in av suitable form. For reasons pointed ut I refer to use asolution and whether.

' concentration is sim- 'il 'e eemed 37% ply a matterof choice. In largescale manufacturing there may be s ome advantage in using a solution offormaldehyde but apparently this isnot trueon a small laboratpry-scaleor pilot plant scale." 30% form ldehyde may tend to decrease anyiormaldehydeloss or make it easier tocontrol' uhreaeted j formaldehydeloss.

a ,large scaleif there is any diff culty with formaldehyde 'losscontrol, onecan use a more dilute form of rorrnaldehyde, for instance, a30% solution The reactionrcan beconducted in an autoclave and of ttemptmade to' remove water until 'the'reaction is over. Generally speaking,suc a ro es i is mu mh r f r e F tem l'a t e eaq ipn doesnotfseemfo gotocompletion, foaming takes place, other mechanical .or chemicaldifficulties are involved I have found noadyar tage in using solidformaldehyde because even here water of reaction is formed.

"d e in g i e th preferre m tho of reaction and particularly from thestandpoint of laboratoryprocedure employing a glass resin pot, when 'thereactionhas proceeded'as one can,rea-. Sammy-expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or dOfC. for a or 5 hours, or at the most, up to -251 hours, I thencomplete the reaction by raising the temperature up to 150 (1., orthereahouts as required. The initial low temperature procedure can beeliminated or reduced to merely the shortest period of time which avoidsloss of amine or formaldehyde. At a higher temperature I use aphase-separating trap and subject the mixture to refluxcondensationuntil the water of reaction and the water of solution of'the formaldehyde is'elirninated. permitvthe temperature toriset'osomewhere about les s iis wi r and, hen forone to threehours; longer.There moval ofthe solventsis oonduetedin a con enqn lrma n r nthe ame Ws t rem v of solventsin resin manufacture as describedin aforementionedU. S, ,Batent N0. 2, i99,368.

. Needless to .say, as fares/the. ratiOll -reafltv ants goes I haveinyariably ernployedapproximately ne 1 f'1 l B$ I winemakeular,,weig ht..of. the resin ,molecule, 2 moles.,-,o f t c nda am ne a 2. 2 1 oformaldehyde. In some instances I have. added a trace of caustic asanadded-catalyst but'havefound ;no particular advantagein this. In othercases I have used a slight excess of formaldehyde and, again, havenot'found any particular advantage in this.- Inothercases I have used, aslight excess of amineand, again, have notfound anyparticular advantageinso doing, Whenever feasible I havechecked the, completeness ofreaction in the usual .ways, including the amount ofwater of reaction,molecular weight, and particularly in some instances have checkedwhetherlornot the endproduct showed surface-activity, particularly in adilute acetic acid. solution. -The nitrogen content after removal ofunreacted amine, i-fany is present, is another index.

In the hereto attached claims reference is made to the product as such,i e., the anhydro basel 't -sa h -hyd ate bas -1 the material as it comb'nes with water orthesalt orm w th a omb nafion 10 suit b ea ds a re ise entia v the am m teria bu merely another form and, thus, .theclaimsare in.- nd --QV 1. t r e f rms it e an yd case, the free base,and.-the salts.

In light of what has been said previously, little more need besaid astotheactual .procedureernpl r r a t n O the he e described condensationproducts. The follow-i-ng example wil Serve b W f i qs a ion Example 1bThe resin soobtained a neutral state had a light amber color.

882 grams of the resin identified as 2a, precedms, were powdered andmixedwith anequal weight of xylene, i. e,, 882 grams. The mixture wasrefluxed until solution wascomplete. It was then adjusted toapproximately 30 to. 35? C., and 146 grams of diethylamineadded. ,Themixture was stirred vigorously and formaldehyde added slowly. Theformaldehydefwas used as. a 37% 91l 0 an 62. arms e m lo ed. h h we e.,adde win, abg i 2. /2 h ur e mi tu 51 kept within atempera- We ran e 3E 55 G .iprabo t 2 .;hou .A

using a phase-separating trap and a small Note that as pointed outpreviously, this proamount of aqueous distillate withdrawn from cedureis illustrated by 24 examples in Table II.

TABLE II Strength Max. Resin Amt of Formal- Solvent gg gg' Dis- Ex. N 0.Used rs Amine Used and Amount dehyde Used and Temp Time till.

g 50111. and Amt. e (hrs Temp.,

Amt. 0. 2a 882 dlethylamine, 146 grams 37%, 162 gxylene, 882 g. 20-25 30150 a 480 diethylamlne, 73 grams 37%, 81 g xylene, 480 g. 22-30 24 1521011 633 o 30%, 100 g xylene, 633 1;. 21-24 38 147 2a 441 dibutylamine,129 grams 37%, 81 gr. xylene,441 g. 25-37 32 149 5a 480 do .do xylene,480 g. 20-24 35 149 a 633 .do d0 xylene, 633 g. 18-23 24 150 2a 882morpholine, 174 grams 37%, 162 g. xylene, 882 g -26 35 145 5a 480morpholine, 87 grams. 37%, 81 g xylene, 480 g. 19-27 24 156 100 633 dod0... xylene, 633g 20-23 24 147 130 473 dioctylamlne(di-2-ethylhexylaminc), 117 grams. 30%, 100 g. xylene, 473 g. 20-21 38148 1411 511 do do xylene, 511 g. 19-20 30 146 1511 665 do 37%, 81 gxylen 665 g. 20-26 24 150 2a 441 (O;H OG,H4OO;H4),NH, 250 grams... 30%,100 g. xylene, 441g. 20-22 31 147 5a 480 (C HtoOzHioG HihNH, 250grams... d0 Xyl ne, 480 g. 20-24 36 148 9a 595 (C H 0C,H40C;H4);NH, 250grams 37%, 81 g xylene, 595 g. 23-28 145 2a 441 (CiHtoOfi CHwH)O(CH;)OHOH9)NH, 361 do xylene, 441 g. 21-23 24 151 grams. 5a 480(C4HtOGHOH(CH )O(CH;) OHCHI)INH, 361 do xylene, 480 g. 20-24 24 150grams. 14a 511 (O34F1IiOCHiGH(OHi)0(CH;) OHCH2)2NH, l00g xylene, 511g.20-22 25 146 6 grams. 220 498 (0311930CHgOHgOCHgOHaOCHzCHzhNH, 37%, 81 gxylene, 498g 20-25 24 140 0 grams. 23a 542(GHEOOHRGHQOCH]OH2OOH]CH2)2NH, do xylene, 542g. 28-38 30 142 "09 grams.250 547 (6119 0CHnCH OOHgOHzOOHgOHQgNH, do l xylene, 547g- 25-30 26 14830 grams. 2a 441 (C11 0CH CHgCHzCHiOHiCHihNH, 245 do xylene, 441g. 20-2228 143 grams. 26a 595 (CHQOOHZCHZCHICHZOH2OHZ)ZNH, 245 30%, l00g xylene,595g- 18-20 25 146 2711 391 19-22 24 145 grams. (C1130CH7CH1CH:CHzCH0Hg)gNH, 98 30%, 50 g xylene, 391ggrams.

, time to time, and the presence of unreacted PART 5 formaldehyde notedAny unreacted formalde' Conventional demulsifying agents employed inhyde seemed to disappear within 2 to 3 hours the treatment of 011 fieldemulslons are used as after refluxmg was started- As as t such, or afterdilution with any suitable solvent,

- of formaldehyde was no longer detectable the 40 such as waterpetroleum hydrocarbons such as phase-separating trap was set so as toeliminate benzene tolune xylene tar acid i cresol all water sqlutlon andreactlon' After the 'anthracene oil, etc. Alcohols, particularly ali-Water was .ehmmated Part the Xylene was phatic alcohols, such as methylalcohol, ethyl z 2 the ii f i reached approxl' alcohol, denaturedalcohol, propyl alcohol, butyl ma 8 y or s 1gb y hlgher' The mass was 5alcohol, hexyl alcohol, octyl alcohol, etc., may be kept at this highertemperature for about 4 hours employed as dfluents' Miscellaneoussolvents .reactlon P r Durmg thls time any such as pine oil, carbontetrachloride, sulfur addit onal watel, which was probably Wat ofdioxide extract obtained in the refining of petroreactlon whlch hadformed, was ellmlnated by leum etc" may be employed as diluents simimfaans of the F The resldual Fylene a larly, the material or materialsemployed as the mltted to stay in the cogenerlc mlxture. A smalldemulsifymg agent f my process may be amount of the sample was heated ona Water mixed with one or more of the solvents cusbath to remove theexcess xylene and the residual t m ily used in connection withconventional nlatenal was dalfk red 60101 and had the demulsifyingagents. Moreover, said material or slstencyPf a Stlcky tacky resin Thematerials may be used alone or in admixture with Overall tlme for thereactlon Was about 30 hoursother suitable well-known classes ofdemulsifying In other examples it varied from 24 hours to 36 agentsT1111? can be reduced by cutting low It is well known that conventionaldemulsifying perature period to approximately 3 to 6 hours. agents maybe used i a water-soluble form, or

Note that in Table II there are in an oil-soluble form, or in a formexhibiting large number of added examples illustrating the both andwaterolubility s ti they e p o e u In e h casethe initial may be used ina form which exhibits relatively u wa l r nd h ld at a f y w m limitedoil-solubility. However, since such reture (30 to 40 C.) for a period ofseveral hours. agents are frequently used in a ratio of 1 to h x n w mplyed until the odor of 65 10,000 or 1 to 20,000, or 1 to 30,000, or even1 yde disappeared. After the odor of to 40,000, or 1 to 50,000 as indesalting practice, d hyd d s ppeared the phase-separating such anapparent insolubility in oil and water is trap was employed to separateout all the water, not significant because said reagents undoubtedlyboth the solution and condensation. After all, have solubility withinsuch concentrations. This the Water had been separated nou h Xyl newas'70 same fact is true in regard to the material or taken out to havethe final product reflux for materials employed as the demulsifyingagent of several hours somewhere in the range of to my process.

0., or thereabouts. Usually the mixture In practicing the presentprocess, the treating yielded a clear solution by the time the bulk ofor demulsifying agent is used in the conventional the water, or all ofthe water, had been removed. 75 way, well known to the art, described,for example, in Patent -2,626,929,da'ted January 27, 1953, Part 3, andreference is .made theretofor a description of conventional proceduresof demulsifying, including batch, continuous, and downthe-holedemulsi-fication, the process essentially involving introducing asmallamount of demulsifier into a large amount of emulsion with adequateadmixture with or without the applicationof heat, and allowing themixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsifier. -A mixture which illustrates such combination is thefollowing:

The product of Example 11), 20%;

A cyclohexylamine salt of a polypropylated naphthalene'monosulfonicacid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic .acid, 24

A sodium salt of oil-soluble -mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol,

Theabove proportions are all weight percents.

The compounds herein described and particularly those adapted forbreaking petroleum emulsions, although having other uses as noted in myco-pending application, Serial No. 288,742, filed May 19, .1952, arederived .from resins in which the bridge between phenolic nuclei is amethylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposesare obtainable from another class of resins, i. 16-, those in which thephenolic nuclei are separated by a radical having at least a Ii-carbonatom chain and are obtained, not by the use of a single aldehyde but bythe use of formaldehyde, in combination with .a carbonyl compoundselected from the class of aldehydes and ketones in which there is analpha hydrogen atom available as in the case of metaldehyde or acetone.Such resins almost invariably involve the use of a basic catalyst.bridge radicals between phenolic nuclei have either hydroxyl radicals orcarbonyl radicals, or both, and are invariablyoxya'lkylation-susceptible and may also enter into more complicatedreactants with basic secondary amines. bridge radical in the initialresin has distinct hydrophile character. Such resins or compounds whichcan be converted readily into such resins are described in the followingpatents. Such analogous compounds are not includedas part of the instantinvention.

U. S. Patents Nos. 2,191,802, February 27, 1940, to Novotny et al.;2,448,664, September 27, 1948, to Fife et al.; 2,538,883, January 23,1951, to Schrimpe; 2,538,884, January '23, 1951, to Schrimpe; 2,545,559,March 20, 1951,130 Schrimpe; 2,570,389, October 9, 1951, to Schrimpe.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is: v

1. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subiecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional SuchThe

said resin :being 20 only in regard to methyl'ol-forming reactivity;:derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being .of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than '24 carbon atomsand substituted in the 2,4,6'p'osition; (b) a basic nonhydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom, and (-0) formaldehyde; saidcondensation reaction being conducted at a temperature 'sufficientlyhigh to eliminate water and below the pyrolytic pointof the reactantsand resultants 'of reaction; and with .the proviso that the resinouscondensation productresu'lting from the process be heatstable andoxya'lkylation-susceptible.

2. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) anoxyalkylationsusceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol forming reactivity; said resin being derived byreaction between a difun'ctional monohydric phenol and an aldehydehaving not *over 8 car- 'bon atoms and reactive toward said phenol; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic nonhydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted .at a temperature sufficiently high toeliminate water .and below the pyrolytic point of the reactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to producea significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehydederived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the further provisothat the ratio of reactants be approximately 1, 2 and 2 respectively;and with the final proviso that the resinous condensation productresulting from the process be heat-stable and oxyalkylation-susceptible.

3. Aprocess for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) an 21oxyalkylation-susceptible, fusible, non-oxygenated organicsolventso1uble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei resin molecule; said resin being difunctional only inregard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic nonhydroxylated secondarymonoamine having not more than 32 carbon atoms in 'any group attached tothe amino nitrogen atom, and (c) formaldehyde; said condensationmolecule; with the added proviso that the ratio of reactants beapproximately 1, 2, and 2, respectively; with the further proviso thatsaid procedure involve the use of a solvent; and with the final provisothat the resinous condensation product resulting from the process beheatstable and oxyalkylation-susceptible.

4. A process for breaking petroleum emulsions of the water-and-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) anoxyethylationsusceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 24 carbon atomsand substituted in the 2,4,6 position; (b) a basic nonhydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom, and (c) formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction, with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the added provisothat the ratio of reactants be approximately 1, 2 and 2, respectively;with the further proviso that said procedure involve the use of asolvent; and with the final proviso that the resinous condensationproduct resultingfrom the process be heat-stable andoxyalkylationsusceptible.

5. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) anoxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having anaverage molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic nonhydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufiiciently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the added proviso that theratio of reactants be approximately l, 2 and 2, respectively; with thefurther proviso that said procedure involve the use of a solvent; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable and oxyalkylation-susceptible.

6. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) anoxyethylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage, phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylolforming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being .being conducted at a weight corresponding to aemamformed .in the substantial absence of ;trifunc in which R is analiphatic hydrocarbon radical atoms and substituted in the 2, position;(b)

a basic nonhydroxylaed secondary monoamine having not more than 32carbon atoms in any group attached to the amino nitrogen atom, and (c)formaledhyde; said condensation reaction temperature above the boilingpoint of water and below 150 C., with the proviso that the condensationreaction be conductedso as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a iQrmaldehyde-deriVed methylenebridge connecting the amino nitrogen atom with a resin molecule; withthe added proviso that the ratio of reactants be approxi- 1 mately 1, 2and 2, respectively; with the further proviso that said procedureinvolve the use of a solvent; and with the final proviso that theresinous condensation product resulting from the process be heat-stableand oxyalkylation-susceptible.

7. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the ess of condensing (a) an oxyethylation-susceptible,fusible, non-oxygenated organic solventsoluble, water-insoluble,low-stage phenol-formaldehyde resin having an average molecular 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of triiunctionalphenols;said phenol being or" the formula in which R, is an aliphatichydrocarbon radical having at least 4 and not more than 14 carbon atoms.and substituted in the para position; (b) a basic nonhydroxylatedsecondary monoamine having not more than 32 carbon :atoms in any groupattached to the amino nitrogen atom, and (0) formaldehyde; saidcondensation reaction being conducted ata temperature above the boil--35 ing point of water and below 156 0., with the proviso that thecondensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the ratio ofreactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible.

products obtained in the procat least 3 and not over emulsion 24 8. Theprocessor cla m 1 with the proviso that the hydrophile properties of theproduct of the condensation reaction employed in the form of a 'memberofthe class consisting of (a) the anhydro base as is, (b) the free base,and (c) the salt of hydroxy acetic acid, in an equal weight of xyleneare sufiicient to produce an emulsion when said xylene solution isshaken vigorously with 1 to 3 volumes of water.

9. The process of claim 2 with the proviso that the hydrophile:properties of the product of the condensation reaction employed in theform of a member ofthe lass consistingof (a) the anhydro base as is, (b)the free base, and (c) the salt of hydroxy acetic acid, in an equalweight of xylene are sufiicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

10. The process of claim 3 with the proviso that the hydrophileproperties of the product-0t the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) thesalt of hydroxy acetic acid, in an equalweight of xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

11. The process of claim 4 with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of hydroxy acetic acid, in an equalweight of xylene are suflicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 5 with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of hydroxy acetic acid, in an equalweight of xylene are sufficient to produce an when said xylene solutionis shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 6 with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a) the anhydro base as is,(b) the free base, and (c) the salt of hydroxy acetic acid, in an equalweight of xylene are sufiicient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 7 with the proviso that the hydrophileproperties of the product of the condensation reaction employed in theform of a member of the class consisting of (a the anhydro base as is,(b) the free base, and '(c) the salt of hydroxy acetic acid, in an equalweight of xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,031,557 Bruson Feb. 18, 1936 2,457,634 Bond et a1 Dec. 28,1948 2,499,365 De Groote et al Mar. '7, 1950 2,499,368 De Groote et a1Mar. 7, 1950 2,570,377 Revukas Oct. 9, 1951

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF CONDENSING (A) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA